Structural and redox properties in thioether-based (N/S) copper(II/I) complexes: Experimental and theoretical investigations

The complexes [CuIN2(SMe)2](ClO4) (1) and [CuIIN2(SMe)2(CF3SO3)2] (2) in both CuI and CuII redox states from N2(SMe)2 ligand (N,N-(2-pyridylmethyl)bis(2-methyl-thiobenzyl)amine) have been synthesized and structurally characterized by X-ray crystallography. Electrochemical studies show that the two complexes interconvert during the one electron transfer. Comparison with another complex with tBu instead Me groups on the thioether ligand shows detectable changes in X-ray structures and in redox properties. Theoretical calculations on the different steps of the redox process have been performed. Values underline steric constraints induced by the substitutions on thioether alkyl groups.

Graphical abstractIn both CuI and CuII redox state copper complexes were synthesized and characterized by Xray crystallography. Experimental and theoretical investigations evidence that small changes in the substitution pattern of the ligand have structural and redox properties consequences.Figure optionsDownload full-size imageDownload as PowerPoint slide